Ethylene vinyl acetate (EVA) copolymers are well-known synthetic materials formed by copolymerizing ethylene and vinyl acetate. EVA copolymers may be crosslinked by free radial generators such as peroxides, azides, or high energy radiation to form elastomeric or flexible articles, depending on the vinyl acetate content. As disclosed in “Levapren® Ethylene Vinyl Acetate (EVM)” literature LXS-KA 017e, 2010-10, 01/2012, EVA copolymer crystallinity and melting point increase with decreasing vinyl acetate content. When the vinyl acetate content is sufficiently low that the melting peak temperature of the EVA copolymer exceeds about 100° C., the EVA copolymer becomes difficult to mix with peroxide without causing scorch or (i.e., premature curing), and if successful, the high crystallinity results in a stiff and inelastic cured article. Therefore, the EVA copolymers useful in this invention have a melting peak temperature less than about 100° C. The ethylene vinyl acetate (EVA) copolymers may contain only copolymerized ethylene units and vinyl acetate units or may comprise copolymerized ethylene units, vinyl acetate units, and additional copolymerized monomers, for example esters of unsaturated carboxylic acids, such as methyl acrylate or butyl acrylate. Examples of commercially available EVA copolymers suitable for use in this invention include certain Elvax® resin products from E. I. du Pont de Nemours and Company and Levapren® products from Lanxess Corp.
In view of their low cost compared to other flexible or elastic polymers, EVA copolymers are widely used in the manufacture of wire and cable jacketing as well as in the production of automotive parts such as hoses and seals.
Resistance to heat aging is a particularly desirable property in rubber parts that are used in under the hood automotive applications, e.g. hoses, gaskets, and seals. Because such parts may be exposed to temperatures in excess of 175° C. for periods of several hours on a regular basis, degradation of physical properties through oxidative embrittlement can occur. In cured ethylene vinyl acetate (EVA) articles, this often results in a reduction in extensibility and an increase in hardness and modulus of the rubber article. Such effects are disclosed for example in EP1081188. Methods to enhance heat resistance, specifically hot air aging resistance, of EVA articles have involved attempts to identify more effective antioxidant systems. However, there is still a need to improve the heat or hot air aging resistance of these copolymers.
It has now been found that it is possible to produce cured EVA articles that exhibit excellent heat aging resistance by dispersing small amounts of polyamide (up to 10 wt %) in the EVA copolymer.
A number of EVA copolymer-polyamide blend compositions have been disclosed in the prior art. For example, it is known to add uncured EVA copolymers (i.e. gums) to polyamides to form toughened thermoplastic compositions. U.S. Pat. No. 4,174,358 exemplifies the use of uncured EVA copolymers at levels up to 20 wt % as toughening additives for polyamides. A compatibilizer such as a maleic anhydride grafted EVA copolymer may also be included in the EVA copolymer-polyamide blend, as disclosed in J. Polymer Science: Part B: Polymer Physics, Vol. 47, 877-887 (2009). The polyamide component in these compositions comprises the continuous polymer matrix and the uncured EVA copolymer is a minor additive. When polyamide comprises the continuous phase in the blend the composition generally cannot be processed at temperatures below the melting temperature of the polyamide, or can be processed only with great difficulty at such temperatures.
It is also known to form thermoplastic elastomer compositions comprising EVA copolymer and polyamide. For example, U.S. Pat. No. 5,948,503 discloses compositions comprising an uncured elastic polymer, a polyamide in the form of fine fibers, and a polyolefin having a melting temperature from 80° C. to 250° C. In addition, certain vulcanized compositions are disclosed therein.
Thermoplastic vulcanizates comprising EVA and polyamide, in which the EVA copolymer is dynamically crosslinked (i.e., crosslinked under shear mixing to create a dispersion of elastomer particles in a continuous phase of another polymer) are also known. Such compositions are disclosed in EP2098566, and may be improved by the use of a coupling agent such as maleic anhydride grafted EVA copolymer as disclosed in U.S. Pat. No. 7,691,943.
U.S. Pat. No. 7,608,216 and U.S. Patent Application Publication 2006/0100368 disclose compositions prepared by admixing an uncured elastomer, for example an EVA copolymer, with a thermoplastic polymer or another uncured (gum) elastomer. Techniques such as fractional curing, partial dynamic vulcanization, or the use of high performance reinforcing fillers are disclosed to increase the green strength of the uncured or partially cured compound. The admixed compositions may be subsequently crosslinked with a curing agent for the elastomer component.
It has now been found that when EVA copolymers having a melting peak temperature of about 100° C. or less additionally comprise about 0.1 wt % to 10 wt % polyamide based on the total weights of EVA copolymer and polyamide in the blend, the resultant compositions, when cured by a free radical generator, exhibit enhanced resistance to physical property loss during hot air aging. In addition, such compositions maintain similar Shore A hardness, tensile strength, tensile elongation to break, and other physical properties of the unmodified cured EVA article.